Tandem photovoltaic device combining a silicon-based sub-cell and a perovskite-based sub-cell comprising a p- or n-type material/perovskite composite layer

Abstract

Tandem photovoltaic device combining a silicon-based sub-cell and a perovskite-based sub-cell comprising a P- or N-type material/perovskite composite layer including: A/a silicon-based sub-cell A; and B/a perovskite-based sub-cell B, comprising at least: —a conductive or semiconductor layer of the N type in the case of a NIP structure, or of the P type in the case of a PIN structure, and—a composite layer, superimposed over the lower conductive or semiconductor layer, comprising at least one perovskite material and at least one material of the P type in the case of a NIP structure or of the N type material in the case of a PIN structure

What is claimed is: 
     
         1 .- 19 . (canceled) 
     
     
         20 . A tandem photovoltaic device, comprising, in this superimposition order:
 A/a silicon-based sub-cell A comprising at least:
 a substrate made of crystalline silicon; and 
 at least one layer, distinct from said substrate, made of N- or P-doped amorphous or polycrystalline silicon; and 
   B/a perovskite-based sub-cell B, comprising at least:
 a conductive or semiconductor layer, called lower layer, of the N type in the case of a NIP structure, or of the P type in the case of a PIN structure, and 
 a composite layer, superimposed over said lower conductive or semiconductor layer, comprising at least one perovskite material and at least one material of the P type in the case of a NIP structure or of the N type material in the case of a PIN structure, and having a gradient of the perovskite material/P material mass ratio in the case of a NIP structure or perovskite material/N material mass ratio in the case of a PIN structure, decreasing in the direction from the interface between said composite layer and said lower conductive or semiconductor layer towards the opposite face of said composite layer, 
   the perovskite-based sub-cell B having a planar structure   
     
     
         21 . The tandem photovoltaic device according to  claim 20 , wherein said sub-cell A is a silicon heterojunction sub-cell or a TOPCon-type architecture sub-cell. 
     
     
         22 . The tandem photovoltaic device according to  claim 20 , wherein said sub-cell A is a silicon heterojunction sub-cell comprising, in this stacking order:
 a first electrode E1 A ;   a layer made of N-doped or P-doped amorphous silicon;   said substrate made of crystalline silicon;   a layer made of P-doped or N-doped amorphous silicon; and   optionally, a second electrode E2 A .   
     
     
         23 . The tandem photovoltaic device according to  claim 20 , wherein said sub-cell A is a TOPCon-type architecture sub-cell, comprising:
 said substrate made of N- or P-doped crystalline silicon;   at the face of the substrate intended to form the rear face of the tandem photovoltaic device, a layer made of highly N +  or P +  doped polycrystalline silicon, said layer made of highly doped polycrystalline silicon being separated from said substrate by a passivation layer made of oxide so-called “tunnel oxide”,   on the side of the opposite face of the substrate, at least one layer made of highly P+ or N+ doped crystalline or polycrystalline silicon of the electrical type opposite to that of the substrate.   
     
     
         24 . The tandem photovoltaic device according to  claim 20 , wherein said perovskite-based sub-cell B comprises, in this stacking order:
 optionally a first electrode E1 B ;   said lower conductive or semiconductor layer of the N type in the case of a NIP structure or of the P type in the case of a PIN structure;   said composite layer comprising at least one perovskite material and at least one material of the P type in the case of a NIP structure or of the N type in the case of a PIN structure, and having a gradient of the perovskite material/P material mass ratio in the case of a NIP structure or perovskite material/N material mass ratio in the case of a PIN structure, decreasing in the direction from the interface between said composite layer and said lower conductive or semiconductor layer towards the opposite face of said composite layer; and   a second electrode, called the upper electrode, E2 B .   
     
     
         25 . The tandem photovoltaic device according to  claim 20 , wherein said perovskite material and said P-type or N-type material form within the composite layer of said perovskite-based sub-cell B, over a thickness of at least 10 nm, an interpenetrating structure, said interpenetrating structure being composed of said P-type or N-type material(s) incorporated into a crystallised perovskite matrix. 
     
     
         26 . The tandem photovoltaic device according to  claim 20 , wherein said composite layer of said perovskite-based sub-cell B has, in the direction from the interface between said composite layer and said underlying conductive or semiconductor layer towards the face of said composite layer, opposite to the interface between the composite layer and the underlying conductive or semiconductor layer:
 a first area primarily formed of the perovskite-type material, or exclusively made up of the perovskite-type material;   an area comprising a mixture of the perovskite and P-type materials in the case of a NIP structure or N-type materials in the case of a PIN structure; and   an area formed primarily of the P-type material in the case of a NIP structure or of the N type material in the case of a PIN structure.   
     
     
         27 . The tandem photovoltaic device according to  claim 20 , wherein the interface between the composite layer and the underlying conductive or semiconductor layer at the sub-cell B forms a planar junction. 
     
     
         28 . The tandem photovoltaic device according to  claim 20 , wherein said composite layer has a thickness smaller than or equal to 1 μm. 
     
     
         29 . The tandem photovoltaic device according to  claim 20 , wherein the perovskite material of said composite layer is of formula ABX 3 , with:
 A representing a cation or a combination of metallic or organic cations;   B representing one or more metallic element(s), chosen among lead, tin, bismuth and antimony; and   X representing one or more halide anion(s).   
     
     
         30 . The tandem photovoltaic device according to  claim 20 , wherein said sub-cell B is:
 of the NIP structure, wherein the P-type material of said composite layer is selected from among π-conjugated conductive or semiconducting polymers; or   of the PIN structure, wherein the N-type material of said composite layer is selected from among N-type metal oxides.   
     
     
         31 . The tandem photovoltaic device according to  claim 22 , said device being of the HET/perovskite type with a 2T structure, comprising, in this superimposition order, at least:
 a sub-cell A, comprising in this superimposition order:   said first electrode denoted E1 A ;   said layer made of N-doped or P-doped amorphous silicon;   said substrate made of crystalline silicon;   said layer made of P-doped or N-doped amorphous silicon;   an electronically conductive or semiconductor intermediate layer, called “recombination layer”;   a sub-cell B comprising
 optionally a first electrode E1 B ; 
 said lower conductive or semiconductor layer of the N type in the case of a NIP structure or of the P type in the case of a PIN structure; 
 said composite layer comprising at least one perovskite material and at least one material of the P type in the case of a NIP structure or of the N type in the case of a PIN structure, and having a gradient of the perovskite material/P material mass ratio in the case of a NIP structure or perovskite material/N material mass ratio in the case of a PIN structure, decreasing in the direction from the interface between said composite layer and said lower conductive or semiconductor layer towards the opposite face of said composite layer; and 
 a second electrode, called the upper electrode, E2 B ; 
   comprising in this superimposition order:   said N-type or P-type conductive or semiconductor layer, and   said perovskite/P material or N material composite layer;   said second electrode.   
     
     
         32 . A method of manufacturing a tandem photovoltaic device according to  claim 20 , comprising at least the following steps:
 (a) making said silicon-based sub-cell A; and   (b) making said perovskite-based sub-cell B, in which said composite layer is formed at the surface of said N-type or P-type lower conductive or semiconductor layer, through at least the following steps:   (i) forming, on the surface of said lower conductive or semiconductor layer, a wet film from a solution of precursors of the perovskite material in one or more solvent(s);   (ii) adding to said wet film of step (i) at least one material of the P type in the case of the formation of a NIP stack, or of the N type in the case of a PIN stack; and   (iii) subjecting the whole to a heat treatment conducive to the elimination of the solvents and the crystallisation of the perovskite material.   
     
     
         33 . The method according to  claim 32 , wherein step (ii) is carried out by depositing, at the surface of said wet film of step (i), a formulation of at least said P-type material in the case of the formation of a NIP stack or N-type material in the case of the formation of a PIN stack, in one or more solvent(s), called “anti-solvents”, in which the perovskite precursors are not soluble. 
     
     
         34 . The method according to  claim 32 , wherein steps (i) and (ii) are carried out consecutively by spin-coating. 
     
     
         35 . The method according to  claim 32 , wherein steps (i) and (ii) are carried out consecutively by spin-coating, step (ii) being carried out without stopping the rotation of the rotating platform of the spin coater. 
     
     
         36 . The method according to  claim 32 , wherein step (iii) is carried out by thermal annealing at a temperature comprised between 60 and 150° C.